Investigation into the Organobismuth Dismutation and Its Use for Rational Synthesis of Heteroleptic Triarylbismuthanes, Ar¹₂Ar²Bi

Organobismuthanes undergo dismutation, a substituent scrambling process, complicating the synthesis of unsymmetrically trisubstituted bismuthanes of the general formula Ar¹₂Ar²Bi. Although the dismutation is a mechanistically diverse phenomenon, at ambient or lower temperatures, dismutation is triggered mainly by an electrophilic bismuth source. Therefore, the selection of the electrophile, Ar¹₂BiX (X = tosylate or iodide if Ar¹ = mesityl) or Ar¹BiX₂ (X = tosylate), and its use in low concentration during the reaction is key to suppressing the dismutation, leading to new, streamlined protocols utilizing direct arylations of Ar¹₂BiX (X = OTs or I) or Ar¹Bi­(OTs)₂ with organozincs affording heteroleptic triarylbismuthanes Ar¹₂Ar²Bi.